Chromium waters

Khangarot, B.S. and D.M. Tripathi. 1990. Gill damage to catfish, Saccobranchus fossilis, following exposure to chromium. Water Air Soil Pollut. 53 379-390. 

FIGURE 21.21 Potential-pH equilibrium diagram for the chromium-water system at 25 °C in solutions not containing chloride. [Figure established considering Cr(OH)3.] (from Ref. 33). 

The formation of malonate and oxalate complexes from [Cr(OH2)6] + involves rate-determining chromium-water bond breaking in an ion-pair in each case. Activation parameters for these two reactions, for formation of the monoglycine complex, and for water exchange at chromium(iii) are all rather similar. The formation of edta complexes of chromium(iii) is more complicated, involving several water displacement and chelation steps. Rates and activation parameters are reported for the tridentate to quinquedentate conversion ... 

The water-gas shift reaction usually suffers from mass transfer limitations similar to the reforming process when fixed-bed catalysts are applied. Levent found catalyst effectiveness factors for high temperature iron/chromium water-gas shift catalysts in the range between 10 and 20% [391]. Giuntaet al. calculated catalyst effectiveness factors lower than 10% for a fixed low temperature water-gas shift catalyst bed [392]. 

Figure F.1 Potential-pH equilibrium diagram for the chromium-water system at 25°C considering the hydrated oxide forms.

Chromium(IH) chloride, chromic chloride, CrClj. Violet solid (Cr plus CI2, hydrate plus SOCI2) only soluble in water in presence of Cr. Forms many complexes including the hydrates [Cr(H20)6]Cl3 - violet, [Cr(H20)jCl]Cl2,H20 - green, [Cr(H20)4Cl2]Cl,2H20 - green. 

The higher chromium fluorides, CrFstrong oxidizing agents, immediately hydrolysed by water,... 

Chromium trioxide. CrOj. Red precipitate from [Cr04p plus cone. H2SO4, m.p. 198 C, loses oxygen at 420" C. CrOa is a powerful oxidizing agent and is used as such. Acidic, gives [Cr04] - with water. 

If the chloride is heated with sodium or potassium dichromate-(VI) and concentrated sulphuric acid, a red gas, chromium(VI) dichloride dioxide, CrOjClj, is evolved if this is passed into water, a yellow solution of a chromate(VI) is formed. 

Chromium(VI) oxide is very soluble in water initially, chromic acid , H2Cr04, may be formed, but this has not been isolated. If it dissociates thus ... 

The chromates of the alkali metals and of magnesium and calcium are soluble in water the other chromates are insoluble. The chromate ion is yellow, but some insoluble chromates are red (for example silver chromate, Ag2Cr04). Chromates are often isomorph-ous with sulphates, which suggests that the chromate ion, CrO has a tetrahedral structure similar to that of the sulphate ion, SO4 Chromates may be prepared by oxidising chromium(III) salts the oxidation can be carried out by fusion with sodium peroxide, or by adding sodium peroxide to a solution of the chromium(IIl) salt. The use of sodium peroxide ensures an alkaline solution otherwise, under acid conditions, the chromate ion is converted into the orange-coloured dichromate ion ... 

The addition of concentrated sulphuric acid to a solid dichromate mixed with a chloride produces a red vapour, chromium(VI)dioxide dichloride, Cr02Cl2 (cf. sulphur dioxide dichloride, SO2CI2). Chromium(VI) dioxide dichloride reacts with water immediately ... 

Hydrated chromium Ill) nitrate is a dark green, very deliquescent solid, very soluble in water. The anhydrous nitrate is covalent. 

Dissolve 1 g. of anthracene in 10 ml. of glacial acetic acid and place in 50 ml. bolt head flask fitted with a reflux water-condenser. Dissolve 2 g. of chromium trioxide in 2 ml. of water and add 5 ml. of glacial acetic acid. Pour this solution down the condenser, shake the contents of the flask and boil gently for 10 minutes. Cool and pour the contents of the flask into about 20 ml. of cold water. Filter off the crude anthraquinone at the pump, wash with water, drain well and dry. Yield, 1 g. Purify by re crystallisation from glacial acetic acid or by sublimation using the semi-micro sublimation apparatus (Fig. 35, p. 62, or Fig. 50, p. 70). 

Equip a I litre three-necked flask with a mechanical stirrer and a thermometer, and immerse the flask in a bath of ice and salt. Place 306 g. (283 ml.) of acetic anhydride, 300 g. (285 ml.) of glacial acetic acid and 25 g. of p-nitrotoluene in the flask, and add slowly, with stirring, 42 5 ml. of concentrated sulphuric acid. When the temperature has fallen to 5°, introduce 50 g. of A.R. chromic anhydride in small portions at such a rate that the temperature does not rise above 10° continue the stirring for 10 minutes after all the chromium trioxide has been added. Pour the contents of the flask into a 3 litre beaker two-thirds filled with crushed ice and almost fill the beaker with cold water. Filter the solid at the pump and wash it with cold water until the washings are colourless. Suspend the product in 250 ml. of cold 2 per cent, sodium carbonate solution and stir mechanically for 10-15 minutes filter (1), wash with cold water, and finally with 10 ml. of alcohol. Dry in a vacuum desiccator the yield of crude p-nitrobenzal diacetate is 26 g. (2),... 

Average Range for Duplicate Samples for Different Concentrations of Chromium in Water... 

The bacterial reduction of Cr(VI) to Cr(III) discussed above is also being used to reduce the hazards of chromium in soils and water (104). 

Protein-Based Adhesives. Proteia-based adhesives are aormaHy used as stmctural adhesives they are all polyamino acids that are derived from blood, fish skin, caseia [9000-71 -9] soybeans, or animal hides, bones, and connective tissue (coUagen). Setting or cross-linking methods typically used are iasolubilization by means of hydrated lime and denaturation. Denaturation methods require energy which can come from heat, pressure, or radiation, as well as chemical denaturants such as carbon disulfide [75-15-0] or thiourea [62-56-6]. Complexiag salts such as those based upon cobalt, copper, or chromium have also been used. Formaldehyde and formaldehyde donors such as h exam ethyl en etetra am in e can be used to form cross-links. Removal of water from a proteia will also often denature the material. 

Ferritic stainless steels depend on chromium for high temperature corrosion resistance. A Cr202 scale may form on an alloy above 600°C when the chromium content is ca 13 wt % (36,37). This scale has excellent protective properties and occurs iu the form of a very thin layer containing up to 2 wt % iron. At chromium contents above 19 wt % the metal loss owiag to oxidation at 950°C is quite small. Such alloys also are quite resistant to attack by water vapor at 600°C (38). Isothermal oxidation resistance for some ferritic stainless steels has been reported after 10,000 h at 815°C (39). Grades 410 and 430, with 11.5—13.5 wt % Cr and 14—18 wt % Cr, respectively, behaved significandy better than type 409 which has a chromium content of 11 wt %. 

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